Patent GB-948678-A (GB)
Title: Process for dyeing and printing textiles
Filed: 1961-11-22
Abstract: Polymer-dyestuff derivatives in which residues of an organic dyestuff are linked by a covalent bond through O or N atoms to high polymers which are not resin precondensates, are used in the dyeing of textile materials.  They may be prepared on the one hand, from water-soluble reactive dyestuffs from the oxazine triphenylmethane, xanthene, nitro, acridone, azo, anthraquinone or phthalocyanine dyestuff series or azo dye precursors having reactive groups may be used and on the other hand from the following polymers: (a) water-soluble and/or alkali-soluble polyhydroxylated materials e.g. methyl and ethyl cellulose, hydroxyethyl and carboxyalkyl-cellulose, the sulphuric acid monoesters of hydroxyethyl cellulose, phosphonomethylated cellulose, polyvinyl alcohol, dextrin, starch, dextrin-starch sodium glycollate, pectins, alginates, gum arabic and guaran, (b) amorphous cellulose having a degree of polymerisation less than 800, (c) insoluble or at most colloidally soluble polyhydroxylated materials, e.g. alkali-insoluble cellulose ethers and esters, weakly carboxylated and weakly phosphonomethylated cellulose, insoluble starch, tragacanth, locust bean flour and (d) polymers containing amino or imino groups, e.g. casein, chitosan, aminoethyl-cellulose aminated starch, aminated cellulose derivatives and aminated dextrin. The reaction of the two components may be carried out in an aqueous suspension in the presence of an acid acceptor e.g. an alkali metal carbonate, bicarbonate or phosphate, at a temperature of 20-100 DEG C. The following polymers are employed in the examples: carboxymethylcellulose (1), polyvinyl alcohol (1), methyl cellulose (2), soluble starch (3), dextrin (4,6,7, and 8), aminated starch (4), casein (4) and wheat starch (7).ALSO:Textiles are dyed or printed by applying an aqueous preparation containing, in solution or in a finely dispersed form (a) a dyestuff derivative in which residues of an organic dyestuff are linked by a covalent bond through O or N atoms to high polymers which are not resin precondensates, and (b) thermocurable resin precondensates and then subjecting the textile to a heat treatment.  The textiles may be composed of fibres of wool, silk, synthetic polyamide and, especially, natural and regenerated cellulose.  The dyestuffs suitable for preparing the derivatives (A) may be water-soluble, e.g. containing -SO3H groups, and should contain a reactive group (many specified) and may be from the oxazine, triphenylmethane, xanthene, nitro, acridone, azo, anthraquinone or phthalocyanine series.  In the case of azo dyes a component thereof may be reacted with the polymer and later converted to the dyestuff.  The specified polymers for the preparation of the derivatives (a) are (A) water-soluble and/or alkali-soluble polyhydroxylated materials, e.g. cellulose methyl or ethyl ether, hydroxyethyl- and carboxyalkyl-cellulose, the sulphuric acid monoesters of hydroxyethyl-cellulose, the reaction product of cellulose with chloromethylphosphinic acid, polyvinyl alcohols, soluble starch, dextrin-starch sodium glycollate, pectins, alginates, and especially sodium alginate, gum arabic and guaran; (B) preferably amorphous, e.g. powdered cellulose having a degree of polymerization below 800; (C) insoluble or at most colloidally soluble polyhydroxylated materials e.g. alkali-insoluble cellulose ethers and esters, weakly carboxylated and weakly phosphonomethylated cellulose, insoluble starch, tragacanth and locust bean flour; and (D) preferably linear polymers containing amino or imino groups, e.g. polyaminostyrenes, polyvinylamine, polyethylene-imine, casein, chitosan, aminoethyl-cellulose, and aminated starch, cellulose derivatives and dextrin.  The reaction of the two components may be carried out in an aqueous suspension in the presence of an acid acceptor, e.g. a carbonate, phosphate or bicarbonate of an alkali metal, at 20-100 DEG C.  Many thermocurable resins (b) are specified from aminoplasts of the urethane, sulphamide dicyandiamide, melamine and urea resin series.  The aqueous preparations may further contain solutions or dispersions of polyvinyl alcohol (not reacted with dyestuff), copolymers of ethylenically unsaturated monomers as well as hydrophobing agents.  The aqueous preparations must further contain an acidic catalyst, e.g. ammonium sulphate, chloride or phosphate or zinc nitrate, and, when it is used for printing, a thickener e.g. starch, dextrin, tragacanth, British gum, cellulose derivatives or especially alginate as well as usual auxiliaries e.g. urea and glycerol.  When the derivatives (a) are water-insoluble it is advantageous to mill them in a ball or swing mill to below 5 m particle size and also to add a pigment binder, e.g. the vinyl compounds aforementioned.  The aqueous preparations are preferably applied in continuous manner, dried below 100 DEG C. and cured at 120-180 DEG C.  The present process may achieve, in addition to dyeing, crease and shrink resistance; permanent calender effects, hydrophobing and other effects. Examples are given.